CN109731600A - A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application - Google Patents
A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application Download PDFInfo
- Publication number
- CN109731600A CN109731600A CN201811604752.3A CN201811604752A CN109731600A CN 109731600 A CN109731600 A CN 109731600A CN 201811604752 A CN201811604752 A CN 201811604752A CN 109731600 A CN109731600 A CN 109731600A
- Authority
- CN
- China
- Prior art keywords
- room temperature
- temperature
- template
- constant temperature
- predecessor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 14
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 14
- 239000010865 sewage Substances 0.000 title claims abstract description 8
- 238000000746 purification Methods 0.000 title claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 231100000719 pollutant Toxicity 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- -1 melamine Amine Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 230000007717 exclusion Effects 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001912 cyanamides Chemical class 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification/photolysis water hydrogen and preparation method and application, the catalyst is using cyanogen aminated compounds or rich nitrogen carbonaceous material as predecessor, using micro-/ nano inorganic salts as template.The template of predecessor and different proportion is subjected to physical mixed, by high-temperature roasting, template, washing, roasting is gone to prepare porous structure catalyst.Environmental-friendly, at low cost, the high chemical and thermal stability of the catalyst, abjection pollutant are high-efficient.
Description
Technical field
The present invention relates to a kind of difunctional friendly carbon nitride photocatalyst of sewage purification/photolysis water hydrogen and preparation methods
And application, belong to environmentally protective catalysis material and waste water control and renewable and clean energy resource field, especially suitable for live with
And industrial sewage purification and all-solid-state visible light responding device energy source.
Background technique
The energy is material base for the survival of mankind, is the important material guarantee of society and sustainable economic development.Closely
Nian Lai, the fast development of world economy, the fast development of modern industrialization, demand of the people to the energy increasingly increase.In order to full
The growing energy demand of foot, consumes the non-renewable fossil energy such as a large amount of coal, petroleum, natural gas, causes serious
Energy crisis and problem of environmental pollution, constrain society development so that the challenge for existence of facing mankind sternness.Cause
This, the development and utilization of solar energy becomes the key solved these problems.Conductor photocatalysis by directly using solar energy come
A series of important chemical reactions are driven, converting highdensity chemistry for the solar energy of low-density can solve energy crisis and temperature
Organic pollutant in room effect or degradation environment or water.Based on photocatalysis, solve energy crisis and in terms of
The tremendous potential shown, therefore, the great attention by countries in the world government.
TiO is found from Japanese Scientists Fujishima and Honda in 19722Photoelectrocatalysis hydrogen production by water decomposition, photocatalysis neck
The core topic in domain is exactly to seek the cheap light of high stable, the photochemical catalyst with high catalytic efficiency and high visible utilization rate.
Semiconductor light-catalyst be mainly inorganic compound currently, traditional, including metal oxide, sulfide, nitride,
Phosphide and its compound etc..But in these traditional semiconductor light-catalysts, have the shortcomings that many: 1. these nothings
Machine semiconductor is mainly the ultraviolet light utilized, and there are no the photocatalysis materials for having high visible utilization rate and high quantization efficiency
Material.2. mostly including expensive yttrium in these semiconductor materials, photocatalysis technology is difficult to realize in reality
The large-scale application of engineering.Therefore, the high element of abundance is further developed and utilized on the earth as novel photocatalysis material
The research of bulk composition, the catalytic nature of these novel photocatalysis materials of further investigated, high stable can be had simultaneously by preparing
The cheap novel photocatalyst of type, high visible utilization rate and high-quantum efficiency becomes the forward position of international photocatalysis field at present
And hot spot.
In recent years, the advantage such as preparation process that organic semiconductor CN is protruded due to it is simple, and thermal stability is good, to environment friend
It is good and to visible light-responded etc., new energy materials preparation and in terms of show bright prospects.
However, the lesser disadvantage of body phase CN specific surface area, largely limits its photocatalytic activity.Therefore, drawn by template
Enter template (SiO2/ Surfactant/block copolymer) its specific surface area can be improved to a certain extent, to improve its catalysis
Activity.However, removing removing template (SiO2) during the etching agent (HF) used not only result in secondary pollution, while can also be to urging
Agent structure damages；Another aspect is miscellaneous since template (Surfactant/block copolymer) can introduce in the course of the polymerization process
Matter carbon causes rich carbon in catalyst, these can all cause the decline of catalyst performance.
Summary of the invention
In order to overcome defect existing for conventional template method, we are by introducing cheap inorganic salts micro-/ nano particle conduct
Template.It is compared with the traditional method, not only significantly improves specific surface area, also effective solution conventional template method is faced
The above problem.Meanwhile this method is economic and environment-friendly, and it is simple and direct, it is easy to produce in enormous quantities.
Another object of the present invention additionally provides the preparation method and application of the catalyst.
A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification/photolysis water hydrogen, the catalyst is with cyanamide
Class or rich nitrogen carbonaceous material are as predecessor, using inorganic salts as template, with the dilute acid soln of no strong oxidizing property/reproducibility
For etching agent, target product is finally obtained.
In some preferred technical solutions: the catalyst is prepared via a method which to obtain:
(1) mixing of predecessor and template
It is ground after predecessor and template are mixed, obtains mixture；
(2) the first time high-temperature roasting of mixture
Mixture after grinding is calcined under the following conditions: firstly, leading to nitrogen half an hour at room temperature, being excluded
Air；Secondly, with the heating rate of 1~10 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, after constant temperature
It is naturally cooling to room temperature, for use；
(3) removal of template
By the mixture grinding after first time high-temperature roasting uniformly and be added excessive dilute acid soln be stirred 8~for 24 hours；
Ethanol washing is first used later with distilled water centrifuge washing to supernatant liquor to neutrality after stirring, is finally putting into drying in baking oven, to
With；
(4) secondary high-temperature roasts
It will be calcined again after the substance grinding uniformly of step (3) after dry, calcination condition is as follows:
Firstly, leading to nitrogen half an hour at room temperature, air is excluded；Secondly, with the heating rate of 1~10 DEG C/min by room temperature liter
Temperature is to 500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target product.
In above-mentioned preparation method: the predecessor that catalyst is prepared in step (1) is the substance of cyanogen aminated compounds or rich nitrogen；
It is preferred that the substance that the cyanogen aminated compounds is cyanamide, the cyanamid dimerization perhaps melamine rich nitrogen be urea or
Thiocarbamide.
In above-mentioned preparation method: the inorganic salts template in step (1) is magnesia, magnesium carbonate or calcium carbonate.
In above-mentioned preparation method: the mass ratio of predecessor and template is 1:1~10；It is preferred that: predecessor and template
Mass ratio is 1:1~6.
In above-mentioned preparation method: the condition of first time high-temperature roasting is to lead to nitrogen half an hour at room temperature, excludes air；Its
It is secondary, with the heating rate of 3~8 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, Temperature fall after constant temperature
To room temperature, for use.
In above-mentioned preparation method: the condition of second of high-temperature roasting is firstly, leading at room temperature nitrogen half an hour, and exclusion is empty
Gas；Secondly, with the heating rate of 3~5 DEG C/min by room temperature to 500~650 DEG C；Finally, 2~4h of constant temperature, after constant temperature from
It so is cooled to room temperature, obtains target product.
A kind of preparation method of carbon nitride photocatalyst, method includes the following steps:
(1) mixing of predecessor and template
It is ground after predecessor and template are mixed, obtains mixture；It is preferred that: the mass ratio of predecessor and template
For 1:1~10；Further preferred: the mass ratio of predecessor and template is 1:1~6.
(2) the first time high-temperature roasting of mixture
Mixture after grinding is calcined under the following conditions: firstly, leading to nitrogen half an hour at room temperature, being excluded
Air；Secondly, with the heating rate of 1~10 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, after constant temperature
It is naturally cooling to room temperature, for use；
(3) removal of template
By the mixture grinding after first time high-temperature roasting uniformly and be added excessive dilute acid soln be stirred 8~for 24 hours；It stirs
Ethanol washing is first used later with distilled water centrifuge washing to supernatant liquor to neutrality after mixing, and is finally putting into drying in baking oven, to
With；
(4) secondary high-temperature roasts
It will be calcined again after the substance grinding uniformly of step (3) after dry, calcination condition is as follows:
Firstly, leading to nitrogen half an hour at room temperature, air is excluded；Secondly, with the heating rate of 1~10 DEG C/min by room temperature liter
Temperature is to 500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target product.
In technical solution of the present invention: the condition of first time high-temperature roasting is to lead to nitrogen half an hour at room temperature, excludes air；Its
It is secondary, with the heating rate of 3~8 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, dropped naturally after constant temperature
It warms to room temperature, for use；
The condition of second of high-temperature roasting is firstly, leading at room temperature nitrogen half an hour, exclusion air；Secondly, with 3~5
DEG C/heating rate of min by room temperature to 500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, is obtained
To target product.
A kind of application of above-mentioned carbon nitride photocatalyst in terms of photocatalytic pollutant degradation and photolysis water hydrogen.
Compared with current method, effective effect of the invention is as follows:
We select can industrialized production cheap inorganic salts micro-/ nano particle as template, method is simple, green
Environmental protection does not cause secondary environmental pollution and causes catalyst structure on the basis of introducing porous structure increasing specific surface area
Destruction, further improve catalytic activity.
When taking rhodamine B (RhB) as the target contaminant in sewage, under visible light illumination, the highest in 60min
Degradation efficiency can be close to 100%.Compared to traditional template, best performance.
Meanwhile under visible light conditions, photocatalysis water hydrogen manufacturing can achieve 760 μm of ol/g/h, while 16 hours
Stability test discovery, activity is still without being substantially reduced.
Detailed description of the invention
Fig. 1 is nitrogen Adsorption and desorption isotherms；
Fig. 2 is the scanning electron microscope (SEM) photograph of porous structure CN-1-3；
Fig. 3 is Photocatalytic Activity for Degradation rhodamine B；
Fig. 4 is visible light photocatalysis water decomposition hydrogen manufacturing.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Embodiment 1
(1) mixing of predecessor and template
By 1g mass dicyandiamide with and 1g MgO mixed according to certain 1:1 ratio, then grind, be uniformly mixed.
(2) the first time high-temperature roasting of mixture
Uniformly mixed mixture is transferred to crucible, is put into tube furnace, in nitrogen (N2) under the conditions of, firstly, room temperature
Logical nitrogen half an hour down, the air in drain, then with the heating rate of 5 DEG C/min by room temperature to 400 DEG C, it is then permanent
Then warm 2h is naturally cooling to room temperature, stand-by after removal.
(3) removal of template
Uniformly by the mixture grinding after first time high-temperature roasting, excessive dilute acid soln is then added, stirs 20h, removal
Template.Then first ethanol washing is finally used, baking oven, 80 DEG C of dryings are put into distilled water centrifuge washing to supernatant liquor to neutrality.
(4) secondary high-temperature roasts
Substance grinding after will be dry in step (3) is uniformly placed again into crucible, is put into tube furnace in nitrogen (N2) item
Under part, firstly, lead to nitrogen half an hour at room temperature, the air in drain, then with the heating rate of 5 DEG C/min by room temperature
To 550 DEG C, then constant temperature 2h, is then naturally cooling to room temperature, finally takes out grinding for use, is named as CN-1-1.
(5) photocatalysis contaminant degradation and photolysis water hydrogen
The rhodamine B solution of 50mg catalyst CN-1-1,50ml 10mg/L, it is seen that light irradiation；50mg catalyst CN-1-
The aqueous solution of 1, the 100ml triethanolamine (as supplied for electronic agent) comprising 10% volume.The degradation efficiency of rhodamine B is in 1h
100%, the efficiency of photolysis water hydrogen is 678 μm of ol/g/h.
Embodiment 2
(1) mixing of predecessor and template
By 1g mass dicyandiamide with and 2g MgO mixed according to certain 1:2 ratio, then grind, be uniformly mixed.
(2) the first time high-temperature roasting of mixture
Uniformly mixed mixture is transferred to crucible, is put into tube furnace, in nitrogen (N2) under the conditions of, firstly, room temperature
Logical nitrogen half an hour down, the air in drain, then with the heating rate of 5 DEG C/min by room temperature to 400 DEG C, it is then permanent
Then warm 2h is naturally cooling to room temperature, stand-by after removal.
(3) removal of template
Uniformly by the mixture grinding after first time high-temperature roasting, excessive dilute acid soln is then added, is stirred overnight, removes
Template.Then first ethanol washing is finally used, baking oven, 80 DEG C of dryings are put into distilled water centrifuge washing to supernatant liquor to neutrality.
(4) secondary high-temperature roasts
Substance grinding after will be dry in step (3) is uniformly placed again into crucible, is put into tube furnace in nitrogen (N2) item
Under part, firstly, lead to nitrogen half an hour at room temperature, the air in drain, then with the heating rate of 5 DEG C/min by room temperature
To 550 DEG C, then constant temperature 2h, is then naturally cooling to room temperature, finally takes out grinding for use, is named as CN-1-2.
(5) photocatalysis contaminant degradation and photolysis water hydrogen
The rhodamine B solution of 50mg catalyst CN-1-2,50ml 10mg/L, it is seen that light irradiation；50mg catalyst CN-1-
The aqueous solution of 2, the 100ml triethanolamines (as supplied for electronic agent) comprising 10% volume.The degradation efficiency of rhodamine B is in 1h
96%, the efficiency of photolysis water hydrogen is 760 μm of ol/g/h.
Embodiment 3
(1) mixing of predecessor and template
By 1g mass dicyandiamide with and 4g MgO mixed according to certain 1:4 ratio, then grind, be uniformly mixed.
(2) the first time high-temperature roasting of mixture
Uniformly mixed mixture is transferred to crucible, is put into tube furnace, in nitrogen (N2) under the conditions of, firstly, room temperature
Logical nitrogen half an hour down, the air in drain, then with the heating rate of 5 DEG C/min by room temperature to 400 DEG C, it is then permanent
Then warm 2h is naturally cooling to room temperature, stand-by after removal.
(3) removal of template
Uniformly by the mixture grinding after first time high-temperature roasting, excessive dilute acid soln is then added, is stirred overnight, removes
Template.Then first ethanol washing is finally used, baking oven, 80 DEG C of dryings are put into distilled water centrifuge washing to supernatant liquor to neutrality.
(4) secondary high-temperature roasts
Substance grinding after will be dry in step (3) is uniformly placed again into crucible, is put into tube furnace in nitrogen (N2) item
Under part, firstly, lead to nitrogen half an hour at room temperature, the air in drain, then with the heating rate of 5 DEG C/min by room temperature
To 550 DEG C, then constant temperature 2h, is then naturally cooling to room temperature, finally takes out grinding for use, is named as CN-1-3 (such as Fig. 3).
(5) photocatalysis contaminant degradation and photolysis water hydrogen
The rhodamine B solution of 50mg catalyst CN-1-3,50ml 10mg/L, it is seen that light irradiation；50mg catalyst CN-1-
The aqueous solution of 3, the 100ml triethanolamines (as supplied for electronic agent) comprising 10% volume.The degradation efficiency of rhodamine B is in 1h
89%, the efficiency of photolysis water hydrogen is 624 μm of ol/g/h.
Comparative example 1
(1) mixing of predecessor and template
1g mass dicyandiamide is taken, then grinding is uniform.
(2) first time high-temperature roasting
Uniform dicyandiamide will be ground and be transferred to crucible, be put into tube furnace, in nitrogen (N2) under the conditions of, firstly, room temperature
Logical nitrogen half an hour down, the air in drain, then with the heating rate of 5 DEG C/min by room temperature to 400 DEG C, it is then permanent
Then warm 2h is naturally cooling to room temperature, stand-by after removal.
(3) dilute acid pretreatment
Uniformly by the substance grinding after first time high-temperature roasting, excessive dilute acid soln is then added, stirs 20h.Then first
With distilled water centrifuge washing to supernatant liquor to neutrality, ethanol washing is finally used, baking oven, 80 DEG C of dryings are put into.
(4) secondary high-temperature roasts
Substance grinding after will be dry in step (3) is uniformly placed again into crucible, is put into tube furnace in nitrogen (N2) item
Under part, firstly, lead to nitrogen half an hour at room temperature, the air in drain, then with the heating rate of 5 DEG C/min by room temperature
To 550 DEG C, then constant temperature 2h, is then naturally cooling to room temperature, finally takes out grinding for use, is named as CN.
Claims (10)
1. a kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification/photolysis water hydrogen, it is characterised in that: the catalysis
Agent is using cyanamide class or rich nitrogen carbonaceous material as predecessor, using inorganic salts as template, with no strong oxidizing property/reproducibility
Dilute acid soln is etching agent, finally obtains target product.
2. carbon nitride photocatalyst according to claim 1, it is characterised in that: the catalyst is prepared via a method which
It arrives:
(1) mixing of predecessor and template
It is ground after predecessor and template are mixed, obtains mixture；
(2) the first time high-temperature roasting of mixture
Mixture after grinding is calcined under the following conditions: firstly, leading to nitrogen half an hour at room temperature, being excluded empty
Gas；Secondly, with the heating rate of 1~10 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, after constant temperature from
It so is cooled to room temperature, for use；
(3) removal of template
By the mixture grinding after first time high-temperature roasting uniformly and be added excessive dilute acid soln be stirred 8~for 24 hours；After stirring
First with distilled water centrifuge washing to supernatant liquor to neutrality, ethanol washing is used later, is finally putting into drying in baking oven, for use；
(4) secondary high-temperature roasts
It will be calcined again after the substance grinding uniformly of step (3) after dry, calcination condition is as follows:
Firstly, leading to nitrogen half an hour at room temperature, air is excluded；Secondly, with the heating rate of 1~10 DEG C/min by room temperature extremely
500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target product.
3. carbon nitride photocatalyst according to claim 2, it is characterised in that: prepare the forerunner of catalyst in step (1)
Object is the substance of cyanogen aminated compounds or rich nitrogen；It is preferred that the cyanogen aminated compounds is cyanamide, cyanamid dimerization or melamine
Amine, the substance of the rich nitrogen are urea or thiocarbamide.
4. carbon nitride photocatalyst according to claim 2, it is characterised in that: the inorganic salts template in step (1) is
Magnesia, magnesium carbonate or calcium carbonate.
5. carbon nitride photocatalyst according to claim 2, it is characterised in that: the mass ratio of predecessor and template is 1:
1~10；It is preferred that: the mass ratio of predecessor and template is 1:1~6.
6. carbon nitride photocatalyst according to claim 2, it is characterised in that: the condition of first time high-temperature roasting is room temperature
Logical nitrogen half an hour down excludes air；Secondly, with the heating rate of 3~8 DEG C/min by room temperature to 350~400 DEG C；Most
Afterwards, 2~4h of constant temperature is naturally cooling to room temperature after constant temperature, for use.
7. carbon nitride photocatalyst according to claim 2, it is characterised in that: headed by the condition of second of high-temperature roasting
First, lead to nitrogen half an hour at room temperature, exclude air；Secondly, with the heating rate of 3~5 DEG C/min by room temperature to 500~
650℃；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target product.
8. a kind of preparation method of carbon nitride photocatalyst, it is characterised in that: method includes the following steps:
(1) mixing of predecessor and template
It is ground after predecessor and template are mixed, obtains mixture；It is preferred that: the mass ratio of predecessor and template is 1:
1~10；Further preferred: the mass ratio of predecessor and template is 1:1~6.
(2) the first time high-temperature roasting of mixture
Mixture after grinding is calcined under the following conditions: firstly, leading to nitrogen half an hour at room temperature, being excluded empty
Gas；Secondly, with the heating rate of 1~10 DEG C/min by room temperature to 350~400 DEG C；Finally, 2~4h of constant temperature, after constant temperature from
It so is cooled to room temperature, for use；
(3) removal of template
By the mixture grinding after first time high-temperature roasting uniformly and be added excessive dilute acid soln be stirred 8~for 24 hours；After stirring
First with distilled water centrifuge washing to supernatant liquor to neutrality, ethanol washing is used later, is finally putting into drying in baking oven, for use；
(4) secondary high-temperature roasts
It will be calcined again after the substance grinding uniformly of step (3) after dry, calcination condition is as follows:
Firstly, leading to nitrogen half an hour at room temperature, air is excluded；Secondly, with the heating rate of 1~10 DEG C/min by room temperature extremely
500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target product.
9. preparation method according to claim 8, it is characterised in that: the condition of first time high-temperature roasting is to lead to nitrogen at room temperature
Gas half an hour excludes air；Secondly, with the heating rate of 3~8 DEG C/min by room temperature to 350~400 DEG C；Finally, constant temperature
2~4h is naturally cooling to room temperature after constant temperature, for use；
The condition of second of high-temperature roasting is firstly, leading at room temperature nitrogen half an hour, exclusion air；Secondly, with 3~5 DEG C/min
Heating rate by room temperature to 500~650 DEG C；Finally, 2~4h of constant temperature, it is naturally cooling to room temperature after constant temperature, obtains target
Product.
10. a kind of carbon nitride photocatalyst described in claim 1 is in terms of photocatalytic pollutant degradation and photolysis water hydrogen
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811604752.3A CN109731600A (en) | 2018-12-26 | 2018-12-26 | A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811604752.3A CN109731600A (en) | 2018-12-26 | 2018-12-26 | A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109731600A true CN109731600A (en) | 2019-05-10 |
Family
ID=66360061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811604752.3A Pending CN109731600A (en) | 2018-12-26 | 2018-12-26 | A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109731600A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560122A (en) * | 2019-08-16 | 2019-12-13 | 徐州工程学院 | Porous carbon nitride material, and preparation method and application thereof |
| CN110683523A (en) * | 2019-10-29 | 2020-01-14 | 广州大学 | Green carbon nitride and preparation method and application thereof |
| CN112337500A (en) * | 2020-12-01 | 2021-02-09 | 南京工业大学 | Interface optimized MOx/g-C3N4Composite photocatalyst and preparation method and application thereof |
| CN114763258A (en) * | 2021-01-12 | 2022-07-19 | 上饶师范学院 | Method for preparing carbon tri-nitrogen four-nanosheet powder by water-soluble salt template method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378173A (en) * | 2016-10-17 | 2017-02-08 | 阜阳师范学院 | CN photocatalyst prepared by template process and preparation method thereof |
| CN108325550A (en) * | 2018-01-22 | 2018-07-27 | 江苏理工学院 | A kind of Preparation method and use of nitrogen-doped graphene quantum dot/zinc oxide/carbonitride composite visible light catalyst |
| CN108671955A (en) * | 2018-05-24 | 2018-10-19 | 西京学院 | A kind of photodissociation aquatic products complex hydroformylation catalyst and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811604752.3A patent/CN109731600A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378173A (en) * | 2016-10-17 | 2017-02-08 | 阜阳师范学院 | CN photocatalyst prepared by template process and preparation method thereof |
| CN108325550A (en) * | 2018-01-22 | 2018-07-27 | 江苏理工学院 | A kind of Preparation method and use of nitrogen-doped graphene quantum dot/zinc oxide/carbonitride composite visible light catalyst |
| CN108671955A (en) * | 2018-05-24 | 2018-10-19 | 西京学院 | A kind of photodissociation aquatic products complex hydroformylation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIANHAI WANG, ET AL.: "Environment-friendly preparation of porous graphite-phase polymeric carbon nitride using calcium carbonate as templates, and enhanced photoelectrochemical activity", 《J. MATER. CHEM. A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560122A (en) * | 2019-08-16 | 2019-12-13 | 徐州工程学院 | Porous carbon nitride material, and preparation method and application thereof |
| CN110683523A (en) * | 2019-10-29 | 2020-01-14 | 广州大学 | Green carbon nitride and preparation method and application thereof |
| CN112337500A (en) * | 2020-12-01 | 2021-02-09 | 南京工业大学 | Interface optimized MOx/g-C3N4Composite photocatalyst and preparation method and application thereof |
| CN114763258A (en) * | 2021-01-12 | 2022-07-19 | 上饶师范学院 | Method for preparing carbon tri-nitrogen four-nanosheet powder by water-soluble salt template method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109731600A (en) | A kind of difunctional environmentally friendly carbon nitride photocatalyst of sewage purification photolysis water hydrogen and its preparation method and application | |
| CN105817253B (en) | The preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material | |
| CN105618098B (en) | A kind of nitrating molybdenum disulfide loaded platinum photo catalyst and preparation method thereof | |
| CN106362774B (en) | A kind of 1D/2D vertical configuration CdS/MoS2Produce the preparation method of hydrogen catalyst | |
| CN104277219B (en) | Photocatalytic material polyimide, as well as preparation method and applications thereof | |
| CN110302824A (en) | Molybdenum doping graphite phase carbon nitride catalyst and its preparation method and application | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN107321372B (en) | CoS nano particle/N doping RGO liberation of hydrogen composite material preparation method | |
| CN109455701A (en) | A kind of preparation method of the highly doped nitrogen phosphorus carbon nanosheet of highly effective hydrogen yield | |
| CN114426278B (en) | Biomass tar-based nitrogen-doped porous carbon modified by nano carbon spheres and preparation method thereof | |
| CN105214710A (en) | A kind of nonmetal composite visible light catalyst g-C of new green environment protection 3n 4the preparation of/SiC and application thereof | |
| CN108855187A (en) | A kind of fluorine richness boron carbon nitrogen catalysis material and its application in efficiently reduction carbon dioxide | |
| CN113019418A (en) | High-activity g-C3N4Photocatalytic material and preparation method and application thereof | |
| CN104971753A (en) | Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof | |
| CN110813347B (en) | Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof | |
| CN113952963B (en) | CuInS based on Co modification 2 Preparation method and application of photocatalyst | |
| CN113058601A (en) | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting | |
| CN112044454A (en) | Biodiesel magnetic solid base catalyst, preparation method and application | |
| CN108054396A (en) | A kind of nitrogen-doped graphene/cobalt protoxide composite material and preparation method thereof | |
| CN112158879A (en) | Method for preparing CdS by low-temperature molten salt method and application of prepared CdS in photocatalysis field | |
| CN101508456A (en) | Method for auxiliary preparation of different-shape nano-cerium oxide with microwave | |
| CN116173987A (en) | CdIn 2 S 4 /CeO 2 Heterojunction photocatalyst, preparation method and application thereof | |
| CN101343082B (en) | Method for preparing solid-oxide fuel battery nano-perovskite type cathode powder | |
| CN110510596A (en) | A kind of preparation and application of the biomass porous carbon material of nitrogen iron codope | |
| CN104888835A (en) | Preparation method and application of BN/WO3 composite photocatalytic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190510 |
|
| RJ01 | Rejection of invention patent application after publication |